US11532805B2 - Method of preparing electrode for secondary battery - Google Patents
Method of preparing electrode for secondary battery Download PDFInfo
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- US11532805B2 US11532805B2 US17/283,784 US202017283784A US11532805B2 US 11532805 B2 US11532805 B2 US 11532805B2 US 202017283784 A US202017283784 A US 202017283784A US 11532805 B2 US11532805 B2 US 11532805B2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0435—Rolling or calendering
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/26—Processes for applying liquids or other fluent materials performed by applying the liquid or other fluent material from an outlet device in contact with, or almost in contact with, the surface
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/26—Processes for applying liquids or other fluent materials performed by applying the liquid or other fluent material from an outlet device in contact with, or almost in contact with, the surface
- B05D1/265—Extrusion coatings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/04—Construction or manufacture in general
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
Definitions
- the present disclosure relates to a method of preparing an electrode for a secondary battery, and more particularly, to a method of preparing an electrode for a secondary battery that can more easily and efficiently prepare an electrode having a multi-layered structure.
- lithium secondary batteries having high energy density and voltage have been commercialized and widely used.
- a lithium secondary battery has a structure in which an electrode assembly, in which a porous separator is interposed between electrodes, that is, a positive electrode and a negative electrode, each of which includes an active material coated on a current collector, is impregnated with a lithium salt-containing electrolyte.
- the electrode is prepared by passing through a mixing step of mixing/dispersing an active material, a binder and a conductive material in a solvent to prepare a slurry, a coating process of coating and drying the slurry onto a current collector in the form of a thin film, and a pressing step of increasing the capacity density of the electrode after the coating step and increase adhesion between the current collector and the active material, thereby forming an electrode-coating layer on a current collector.
- the electrode mixture portion in contact with the current collector needs to transfer electrons to the active material farther away from the current collector, and so it is required to have high electron conductivity, whereas the electrode mixture portion far from the current collector is required to have excellent impregnation property of an electrolyte and ionic conductivity with the electrolyte, and should be advantageous in discharging gas that may occur during the charge/discharge process.
- the above-mentioned problem can be solved through electrodes having a multi-layered structure in which the sizes of particles constituting the active material is different for each layer.
- the electrode in order to increase the capacity and density of the secondary battery, the electrode can be composed of two active material layers. For example, an electrode has been proposed in which one active material layer is a high power layer so that a fast movement speed of lithium ions can be secured, and another active material layer is formed into a high energy layer to ensure a high energy density.
- each time each layer is formed the coating, drying, and rolling processes have to be repeated, and thus a complicated process is required. As the number of layers required becomes larger, the manufacturing process is more complicated.
- the problem to be solved by the embodiments of the present disclosure is directed to solve the above-mentioned problems, and an object thereof is to provide a method of preparing an electrode for a secondary battery that can easily and efficiently prepare an electrode having a multi-layered structure without a complicated process, while preventing an alignment error between layers or an intermixing phenomenon that may occur during the preparing process.
- a method of preparing an electrode for a secondary battery comprising the steps of:
- the first solvent may be a polar solvent
- the second solvent may be a non-polar solvent
- the first active material may be polar, and the second active material may be non-polar.
- the first solvent may include water
- the second solvent may include at least one selected among propanol, pentanol, butanol, hexanol, ethylene glycol, propylene glycol, diethylene glycol and glycerol.
- the first slurry and the second slurry may be simultaneously coated onto the current collector in a state of being not mixed with each other in the single coating device.
- the stacking order of the first layer and the second layer may be determined by a difference in density between the first slurry and the second slurry.
- the first slurry and the second slurry are discharged through a coating port in the single coating device, and then coated onto the current collector.
- a boundary between the first slurry and the second slurry in the single coating device may be located inside the coating port.
- the first slurry and the second slurry may be respectively injected into the single coating device from separate mixers.
- the flow rates per unit time at which the first slurry and the second slurry are injected into the single coating device from the separate mixers may be identical to each other.
- the first slurry and the second slurry may be injected together into to a single coating device through a single pipe from a single mixer.
- a boundary between the first slurry and the second slurry may be located inside the single pipe.
- the method may include a drying step of simultaneously drying the first layer and the second layer coated onto the current collector.
- the method may include a rolling step of simultaneously rolling the first layer and the second layer coated onto the current collector to form a first active material layer and a second active material layer.
- a plurality of active material layers are formed by using solvents that are not mixed with each other and can form a layered structure due to the difference in polarity, it is not necessary to repeatedly perform steps such as coating, drying, and rolling, whereby the preparation process can be simplified, the alignment error of each layer can be minimized, and the intermixing phenomenon at an interface between layers can be prevented.
- FIG. 1 is a view for explaining a method of preparing an electrode for a secondary battery according to an embodiment of the present disclosure.
- FIG. 2 is a view for explaining a method of preparing an electrode for a secondary battery according to another embodiment of the present disclosure.
- FIG. 1 is a view for explaining a method of preparing an electrode for a secondary battery according to an embodiment of the present disclosure.
- the method of preparing an electrode for a secondary battery includes a step of injecting a first slurry and a second slurry in a second solvent into a single coating device 100 .
- the first slurry can be prepared by dissolving a first active material together with a binder and a conductive material in a first solvent, thereby mixing and dispersing them in the first solvent.
- the second slurry can be prepared by dissolving a second active material together with a binder and a conductive material in a second solvent, thereby mixing and dispersing them in the second solvent.
- the first solvent and the second solvent are preferably separated from each other without being mixed with each other in a single coating device 400 .
- the first solvent and the second solvent have mutually different physical properties.
- the first solvent may be a polar solvent
- the second solvent may be a non-polar solvent
- the first active material dissolved in the first solvent is polar
- the second active material dissolved in the second solvent may be non-polar.
- the non-polar active material mainly consists of a positive electrode active material containing lithium, and specific materials thereof will be described later.
- the non-polar solvent preferably includes at least one selected among propanol, pentanol, butanol, hexanol, ethylene glycol, propylene glycol, diethylene glycol and glycerol, and the polar solvent preferably includes water.
- the first slurry and the second slurry may not be mixed even in the single coating device 400 .
- a step of coating the first and the second slurry onto a current collector 300 through the single coating device 400 is performed. Specifically, the first slurry and the second slurry are coated simultaneously onto the current collector 300 from a single coating device 400 , and more specifically, the first slurry and the second slurry are discharged through one coating port from a single coating device 400 and then coated onto the current collector 300 . Thereby, the layered structure of a first layer 100 containing the first slurry and a second layer 200 ) containing the second slurry can be formed.
- the first slurry and the second slurry form a layered structure without being mixed with each other in the same storage tank, and can be located in a single coating device 400 .
- the layered structure of the first layer 100 and the second layer 200 may be formed on the current collector 300 .
- the first slurry and the second slurry can be coated simultaneously, an alignment error between the first layer 100 containing the first slurry and the second layer 200 containing the second slurry can be significantly reduced, and the complicated process required for preparing multi-layered electrodes can be simplified.
- an intermixing phenomenon in which constituent materials of slurries having flowability are mixed with each other beyond a boundary through an interface between layers may become a problem.
- the intermixing phenomenon at the interface between the first layer 100 and the second layer 200 can be effectively prevented due to the difference in polarity between the first slurry and the second slurry.
- the stacking order of the layered structures in which the first layer 100 containing the first slurry and the second layer 200 containing the second slurry are formed may be determined by a difference in density between the first slurry and the second slurry. For example, depending on the density difference, a polar solvent may be located at the bottom, and a non-polar solvent may be located at the top. Conversely, a polar solvent may be located at the top, and a non-polar solvent may be located at the bottom.
- FIG. 1 a method of preparing an electrode having a two-layer structure in which the first layer 100 and the second layer 200 are formed is illustrated for convenience of description, but it is needless to say that two or more electrodes of multi-layered structures may be prepared according to the same principle, if necessary.
- the conventional method needs to perform coating, drying, and rolling every time, or requires a coating injection nozzle depending on the number of slurries, which makes the process complicated and needs more time and cost.
- the method of preparing an electrode according to the present embodiment can provide an electrode having a multi-layered structure in which the boundaries are divided in a much simpler and efficient manner.
- the first active material constituting the first slurry and the second active material constituting the second slurry may be the material identical to or different from each other depending on the required multi-layered electrode.
- the first active material and the second active material are composed of the same material, but the size of the active material particles and the content of the conductive material may be set so as to be different.
- the concentrations of the first active material and the second active material may be configured to be different, and the first active material and the second active material may be composed of different materials.
- the boundary between the first slurry and the second slurry is located inside the coating port of the single coating device 400 . This will be described in detail below with reference to FIGS. 1 and 2 .
- the layered structure should be formed without being mixed in the single coating device 400 , and by injecting the first slurry and the second slurry at the same pressure through the single coating device 400 , the first slurry and the second slurry are preferably coated onto the current collector 300 while maintaining the state of the layered structure.
- the thickness of the coated first layer 100 and second layer 200 can be set so as to be different from each other.
- the first slurry and the second slurry may be injected into the single coating device 400 from separate mixers 510 and 520 , respectively.
- the first slurry is prepared by mixing and dispersing the first active material together with a binder and a conductive material in a first solvent and the second slurry is prepared by mixing and dispersing the second active material together with a binder and a conductive material in a second solvent.
- Each of the first slurry and the second slurry may be prepared through stirring in the first mixer 510 and the second mixer 520 , and furthermore, storage can be achieved. At this time, in order to prevent the slurry from solidifying, stirring may be performed even during storage.
- first slurry and the second slurry are prepared in separate devices, and then only storage may be performed in the first mixer 510 and the second mixer 520 , respectively.
- the first slurry and the second slurry are respectively injected into the single coating device 400 via a first pipe 610 and a second pipe 620 from the first mixer 510 and the second mixer 520 , and at this time, the flow rate per unit time is preferably identical to each other. Otherwise, the boundary between the first slurry and the second slurry cannot be located inside the coating port in the single coating device 400 , and the first slurry and the second slurry may not be coated simultaneously.
- the dotted line in FIG. 1 means a boundary between the first slurry and the second slurry in the single coating device 400 .
- a boundary represented by a dotted line
- the first slurry and the second slurry may be located inside the coating port of the single coating device 400 .
- FIG. 2 is a view for explaining a method of preparing an electrode for a secondary battery according to another embodiment of the present disclosure.
- a first slurry and a second slurry may be injected into a single coating device 400 from a single mixer 530 .
- the prepared first slurry and second slurry may be stored together in a single mixer 530 . Similarly, in order to prevent the slurry from solidifying, stirring may be performed even during storage.
- the first shiny and the second slurry are injected into a single coating device 400 via a single pipe 630 from a single mixer 530 , it is preferable that a boundary, between the first slurry and the second slurry is located inside the single pipe 630 . Otherwise, the flow rates of the first slurry and the second slurry flowing through the single pipe 630 are not identical and thus, the boundary between the first slurry and the second slurry cannot be located inside the coating port in the single coating device 400 .
- the dotted line in FIG. 2 means a boundary between the first slurry and the second slurry in the single coating device 400 .
- a boundary represented by a dotted line between the first slurry and the second slurry must be located inside the single pipe 630 .
- a step of drying the first layer 100 and the second layer 200 coated onto the current collector 300 may be performed.
- drying can be performed at the same time.
- a rolling step of simultaneously rolling the dried first layer 100 and the second layer 200 to increase the capacity density of the electrode and increase the adhesion between the current collector 300 and the active material may be continued.
- the drying step can be performed at the same time, the preparation process for preparing the electrode having the multi-layered structure can be simplified more efficiently, wasted time and money can be saved, and the extent of drying of each of the multilayer structures can be effectively adjusted.
- the electrode for a secondary battery prepared according to the present embodiments includes a positive electrode and a negative electrode.
- the positive electrode is prepared, for example, by coating and then drying a mixture of a positive electrode active material, a conductive material, and a binder onto a positive electrode current collector and/or an extension current collector, and if necessary, the mixture may further a filler.
- the positive electrode current collector and/or the extension current collector may be formed to a thickness of 3 to 500 micrometers.
- the positive electrode current collector and the extension current collector are not particularly limited as long as a corresponding battery has high conductivity while a chemical change is not caused in the battery, and for example, may be formed of stainless steel, aluminum, nickel, titanium, baked carbon, or aluminum, or a material formed by surface-treating a surface of stainless steel with carbon, nickel, titanium, silver, or the like.
- the positive electrode current collector and the extension current collector may have fine protrusions and depressions formed on a surface thereof to enhance adherence of a positive electrode active material, and may be formed in various forms such as a film, a sheet, a foil, a net, a porous body, a foaming body, and a non-woven fabric structure.
- the conductive material is added in an amount of 1 to 30% by weight based on the total weight of the mixture containing the positive electrode active material.
- the conductive material is not particularly limited as long as a corresponding battery has high conductivity while a chemical change is not caused in the battery, and for example, graphite such as natural graphite and artificial graphite; carbon blacks such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black; conductive fibers such as carbon fiber and metal fiber; metal powders such as carbon fluoride powder, aluminum powder, and nickel powder; conductive whiskey such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; conductive materials such as polyphenylene derivatives may be used.
- the binder is a component that facilitates coupling of an active material, a conductive material, and the like, coupling of a current collector, and typically, may be added in an amount of 1 to 30% by weight based on a total weight of the mixture containing the positive electrode active material.
- binder may include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC) starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated EPDM, styrene styrene rubber, fluorine rubber, and various copolymers.
- CMC carboxymethyl cellulose
- EPDM ethylene-propylene-diene polymer
- EPDM ethylene-propylene-diene polymer
- EPDM ethylene-propylene-diene polymer
- sulfonated EPDM styrene styrene rubber
- fluorine rubber fluorine rubber
- the filler may be optionally used as a component for suppressing expansion of a positive electrode, and is not particularly limited as long as the filler is a fibrous material while a chemical change is not caused in the battery.
- the filler is a fibrous material while a chemical change is not caused in the battery.
- (Actinic polymers such as polyethylene and polypropylene, and fibrous materials such as glass fibers and carbon fibers are used.
- the negative electrode is produced by coating and drying a negative electrode active material on a negative electrode current collector and/or an extension current collector, and if necessary, may optionally and further include the above-mentioned components.
- the negative electrode current collector and/or the extension current collector may be formed to a thickness of 3 to 500 micrometers.
- the negative electrode current collector and/or the extension current collector are not particularly limited as long as a corresponding battery has high conductivity while a chemical change is not caused in the battery, and for example, may be formed of copper, stainless steel, aluminum, nickel, titanium, or baked carbon, or a material formed by surface-treating g a surface of copper or stainless steel with carbon, nickel, titanium, silver, or the like, or may use an aluminum-cadmium alloy or the like.
- the negative electrode current collector and the extension current collector may have fine protrusions and depressions formed on a surface thereof to enhance adherence of a negative electrode active material, and may be formed in various forms such as a film, a sheet, a foil, a net, a porous body, a foaming body, and a non-woven fabric structure.
- the negative electrode active material may include carbons such as hardly graphitizable carbon and graphite-based carbon; metal composite oxides such as Li x Fe 2 O 3 (0 ⁇ x ⁇ 1), Li x WO 2 (0 ⁇ x ⁇ 1), Sn x Me 1-x Me′ y O z (Me:Mn, Fe, Pb, Ge; Me′:Al, B, P, Si, Group 1, 2, 3 elements in the periodic table, halogen; 0 ⁇ x ⁇ 1; 1 ⁇ y ⁇ 3; 1 ⁇ z ⁇ 8); lithium alloys; silicon-based alloys; tin-based alloys; metal-based oxides such as SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , GeO, GeO 2 , Bi 2 O 3 , Bi 2 O 4 , Bi 2 O 5 ; a conductive polymer such as polyacetylene
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Abstract
Description
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- injecting a first slurry prepared by dissolving a first active material in a first solvent and a second slurry prepared by dissolving a second active material in a second solvent into a single coating device; and
- coating the first slurry and the second slurry onto a current collector through the single coating device,
- wherein the first solvent and the second solvent have mutually different physical properties, and form a layered structure of a first layer including the first slurry and a second layer including the second slurry on the current collector, respectively.
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- 100: first layer
- 200: second layer
- 300: current collector
- 400: single coating device
Claims (11)
Applications Claiming Priority (3)
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KR10-2019-0020504 | 2019-02-21 | ||
KR1020190020504A KR102445275B1 (en) | 2019-02-21 | 2019-02-21 | Method of preparing electrode for secondary battery |
PCT/KR2020/000940 WO2020171391A1 (en) | 2019-02-21 | 2020-01-20 | Method of preparing electrode for secondary battery |
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US20210391565A1 US20210391565A1 (en) | 2021-12-16 |
US11532805B2 true US11532805B2 (en) | 2022-12-20 |
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US (1) | US11532805B2 (en) |
EP (1) | EP3846254B1 (en) |
KR (1) | KR102445275B1 (en) |
CN (1) | CN112740440B (en) |
HU (1) | HUE067363T2 (en) |
WO (1) | WO2020171391A1 (en) |
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CN114725312A (en) * | 2022-04-29 | 2022-07-08 | 三一技术装备有限公司 | Dry-process pole piece and preparation method thereof |
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US20210391565A1 (en) | 2021-12-16 |
HUE067363T2 (en) | 2024-10-28 |
EP3846254A4 (en) | 2022-01-05 |
EP3846254B1 (en) | 2024-06-19 |
CN112740440B (en) | 2024-04-16 |
KR102445275B1 (en) | 2022-09-19 |
WO2020171391A1 (en) | 2020-08-27 |
KR20200102193A (en) | 2020-08-31 |
CN112740440A (en) | 2021-04-30 |
EP3846254A1 (en) | 2021-07-07 |
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